Substituted naphthopyrans

Abstract

Described are novel reversible photochromic 2H-naphtho[1,2-b]pyran compounds, examples of which are compounds having certain substituents at the number 5 carbon atom of the naphtho portion of the naphthopyran and at the 2-position of the pyran ring. Certain substituents may also be present at the number 6, 7, 8, 9 or 10 carbon atoms of the naphtho portion of the naphthopyran. Also described are organic host materials that contain or that are coated with such compounds. Articles such as ophthalmic lenses or other plastic transparencies that incorporate the novel naphthopyran compounds or combinations thereof with complementary photochromic compounds, e.g., spiro(indoline) type compounds, are also described.

We claim: 
     
       1. A naphthopyran compound represented by the following graphic formula: ##STR11## wherein, (a) R 1  is selected from the group consisting of --CH 2  X and --C(O)Y, wherein X is halogen, hydroxy, benzoyloxy, C 1  -C 6  alkoxy, C 2  -C 6  acyloxy, amino, C 1  -C 6  mono-alkylamino, C 1  -C 6  dialkylamino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, trimethylsilyloxy, or the group, --OCH(R 11 )Z, Y is the group, --OCH(R 11 )Z, or an unsubstituted, mono-substituted, or di-substituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, 1-pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, pyrazolidyl, pyrazolinyl and 1-piperazinyl, wherein Z is --CN, --CF 3 , halogen, --C(O)R 12 , or --COOR 12 , R 11  and R 12  are hydrogen or C 1  -C 6  alkyl; said heterocyclic ring substituents being selected from C 1  -C 6  alkyl and C 1  -C 6  alkoxy, and said halogen being chloro or fluoro; (b) R 2  and each R 3  are hydrogen, C 1  -C 6  alkyl, C 3  -C 7  cycloalkyl, unsubstituted, mono-, di-, or tri-substituted phenyl, the group, --OR 6 , wherein R 6  is hydrogen, (C 1  -C 6 )alkyl, phenyl(C 1  -C 3 )alkyl, mono-substituted phenyl(C 1  -C 3 )alkyl, (C 1  -C 6 )alkoxy(C 2  -C 4 )alkyl, C 3  -C 7  cycloalkyl, mono(C 1  -C 4 )alkyl substituted C 3  -C 7  cycloalkyl, C 1  -C 6  haloalkyl, allyl, the group, --CH(R 7 )W, wherein W is --CN, --CF 3 , halogen, --C(O)R 7 , or --COOR 7 , wherein R 7  is hydrogen, C 1  -C 6  alkyl, or (C 1  -C 6 )alkoxy(C 2  -C 4 )alkyl, or R 6  is the group, --C(O)T, wherein T is hydrogen, C 1  -C 6  alkyl, C 1  -C 6  alkoxy, the substituted or unsubstituted aryl groups phenyl or naphthyl, phenoxy, C 1  -C 6  mono-or di-alkyl substituted phenoxy, C 1  -C 6  mono-or di-alkoxy substituted phenoxy, each of said phenyl or naphthyl substituents being C 1  -C 6  alkyl, C 1  -C 6  alkoxy or halogen, each of said halogen or halo substituents being chloro or fluoro and n is selected from the integers 0, 1, 2, and 3; and   (c) B and B' are each selected from the group consisting of: (i) the unsubstituted, mono-, di-, and tri-substituted aryl groups phenyl and naphthyl;   (ii) the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzothienyl, dibenzofuranyl, and carbazolyl, said aryl and heterocyclic substituents being selected from the group consisting of hydroxy, amino, C 1  -C 6  monoalkylamino, C 1  -C 6  dialkylamino, morpholino, piperidino, 1-indolinyl, pyrrolidyl, 1-imidazolidyl, 2-imidazolin-1-yl, 2-pyrazolidyl, pyrazolinyl, 1-piperazinyl, C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy, mono(C 1  -C 6 )alkoxy(C 1  -C 4 )alkyl, acryloxy, methacryloxy, and halogen, said halogen or (halo) group being fluoro or chloro;   (iii) the groups represented by the following graphic formulae: ##STR12## wherein D is carbon or oxygen and E is oxygen or substituted nitrogen, provided that when E is substituted nitrogen, D is carbon, said nitrogen substituent being selected from the group consisting of hydrogen, C 1  -C 6  alkyl, and C 2  -C 6  acyl; each R 8  is C 1  -C 6  alkyl, C 1  -C 6  alkoxy, hydroxy, chloro or fluoro; R 9  and R 10  are each hydrogen or C 1  -C 6  alkyl; and m is the integer 0, 1, or 2;   (iv) C 1  -C 6  alkyl, C 1  -C 6  haloalkyl, C 1  -C 6  alkoxy(C 1  -C 4 )alkyl, C 3  -C 6  cycloalkyl, mono(C 1  -C 6 ) alkoxy(C 3  -C 6 )cycloalkyl, mono(C 1  -C 6 )alkyl(C 3  -C 6 )cycloalkyl, and halo(C 3  -C 6 )cycloalkyl, said halo groups being fluoro or chloro; and   (v) the group represented by the following graphic formula: ##STR13## wherein U is hydrogen or C 1  -C 4  alkyl, and V is selected from the unsubstituted, mono-, and di-substituted members of the group consisting of naphthyl, phenyl, furanyl, and thienyl, wherein the substituents for each member of said group are C 1  -C 4  alkyl, C 1  -C 4  alkoxy, fluoro, or chloro; or   (vi) B and B' taken together form an unsubstituted, mono-, or di-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C 3  -C 12  spiro-monocyclic hydrocarbon rings, saturated C 7  -C 12  spiro-bicyclic hydrocarbon rings, and saturated C 7  -C 12  spiro-tricyclic hydrocarbon rings, said fluoren-9-ylidene substituents being selected from the group consisting of C 2  -C 4  alkyl, C 1  -C 4  alkoxy, fluoro and chloro.     
     
     
       2. The naphthopyran of claim 1 wherein: (a) R 1  is selected from the group consisting of --CH 2  X and --C(O)Y, wherein X is hydroxy, C 1  -C 4  alkoxy, or C 2  -C 4  acyloxy, Y is the group, --OCH(R 11 )Z, or an unsubstituted or mono-substituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, piperidino, and 1-pyrrolidyl, wherein Z is --CN, --C(O)R 12 , or --COOR 12 , R 11  and R 12  are hydrogen or C 1  -C 4  alkyl; said heterocyclic ring substituents being selected from C 1  -C 4  alkyl and C 1  -C 4  alkoxy;   (b) R 2  and each R 3  are hydrogen, C 1  -C 4  alkyl, unsubstituted, mono-, di-, or tri-substituted phenyl, the group, --OR 6 , wherein R 6  is C 1  -C 4  alkyl or the group, CH(R 7 )W, wherein W is --COOR 7 , and R 7  is hydrogen or C 1  -C 4  alkyl, said phenyl substituents being C 1  -C 4  alkyl, C 1  -C 4  alkoxy or fluoro and n is selected from the integers 0, 1, and 2; and   (c) B and B' are each selected from the group consisting of: (i) unsubstituted, mono-, di-, and tri-substituted phenyl;   (ii) the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzothienyl, dibenzofuranyl, and carbazolyl, each of said phenyl and heterocyclic substituents being selected from the group consisting of morpholino, piperidino, C 1  -C 4  alkyl, C 1  -C 4  alkoxy, and halogen, said halogen or (halo) group being fluoro or chloro;   (iii) the groups represented by the following graphic formula: ##STR14## wherein D is carbon and E is oxygen; each R 8  is C 1  -C 4  alkyl, C 1  -C 4  alkoxy, hydroxy, or halogen, said halogen being chloro or fluoro; R 9  and R 10  are each hydrogen or C 1  -C 4  alkyl; and m is the integer 0, 1, or 2;   (iv) C 1  -C 4  alkyl, C 1  -C 6  alkoxy(C 1  -C 4 )alkyl, and C 3  -C 6  cycloalkyl; and   (v) the group represented by the following graphic formula: ##STR15## wherein U is hydrogen or methyl, and V is phenyl or mono-substituted phenyl, said phenyl substituent being C 1  -C 4  alkyl, C 1  -C 4  alkoxy, or fluoro; or   (vi) B and B' taken together form an unsubstituted or mono-substituted fluoren-9-ylidene or a member selected from the group consisting of saturated C 3  -C 8  spiro-monocyclic hydrocarbon rings, saturated C 7  -C 10  spiro-bicyclic hydrocarbon rings, and saturated C 7  -C 10  spiro-tricyclic hydrocarbon rings.     
     
     
       3. The naphthopyran of claim 2 wherein: (a) R 1  is the group, --CH 2  X, or --C(O)Y, wherein X is hydroxy, C 1  -C 4  alkoxy, or C 2  -C 4  acyloxy and Y is an unsubstituted or mono-substituted heterocyclic ring selected from the group consisting of 1-indolinyl, morpholino, and piperidino;   (b) R 2  and each R 3  are hydrogen, C 1  -C 2  alkyl, unsubstituted, mono-, di-, or tri-substituted phenyl, the group, --OR 6 , wherein R 6  is C 1  -C 2  alkyl or the group, --CH(R 7 )W, wherein W is --COOR 7 , and R 7  is C 1  -C 2  alkyl, said phenyl substituents being C 1  -C 2  alkyl, C 1  -C 2  alkoxy or fluoro, and n is selected from the integers 0, 1, and 2; and   (c) B and B' are each selected from the group consisting of: (i) unsubstituted, mono-, and di-substituted phenyl;   (ii) the unsubstituted, mono- and di-substituted heterocyclic aromatic groups pyridyl, benzofuran-2-yl, benzothien-2-yl, dibenzothienyl, and dibenzofuranyl, each of said phenyl and heterocyclic substituents being selected from the group consisting of morpholino, piperidino, C 1  -C 2  alkyl, and C 1  -C 2  alkoxy; and   (iii) the groups represented by the following graphic formula: ##STR16## wherein D is carbon and E is oxygen; each R 8  is C 1  -C 2  alkyl, C 1  -C 2  alkoxy or fluoro; R 9  and R 10  are each hydrogen or C 1  -C 2  alkyl; and m is the integer 0, 1, or 2; or   (iv) B and B' taken together form fluoren-9-ylidene, bornylidene, norbornylidene, bicyclo[3.3.1]nonan-9-ylidene or adamantylidene.     
     
     
       4. The naphthopyran of claim 3 wherein R 1  is hydroxymethyl, acetoxymethyl, morpholinocarbonyl, or piperidinocarbonyl; R 2  and each R 3  are hydrogen, phenyl, methoxy, or methyl; and B and B' are each phenyl, methoxy substituted phenyl, morpholino substituted phenyl, dibenzofuran-2-yl, or 2,3-dihydrobenzofuran-5-yl. 
     
     
       5. A naphthopyran compound selected from the group consisting of: (a) 2,2-bis (4-methoxyphenyl)-5-hydroxymethyl-6-methyl-9-methoxy-2H -naphtho[1,2-b]pyran;   (b) 2,2-bis (4-methoxyphenyl)-5-hydroxymethyl-6-phenyl-2H-naphtho[1,2-b]pyran;   (c) 2,2-bis (4-methoxyphenyl)-5-acetoxymethyl-6-phenyl-2H -naphtho[1,2-b]pyran;   (d) 2-(4-methoxyphenyl)-2-(2,3-dihydrobenzofuran-5-yl)-5-piperidinocarbonyl-6-methyl-9-methoxy-2H-naphtho[1,2-b]pyran;   (e) 2,2-bis(4-methoxyphenyl)-5-hydroxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran;   (f) 2,2-diphenyl-5-methoxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran;   (g) 2,2-spiroadamantylene-5-acetoxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran;   (h) 2,2-bis(4-methoxyphenyl)-5-trimethylsilyloxymethyl-6-methoxy-2H-naphtho[1,2-b]pyran;   (i) 2-(4-methoxyphenyl)-2-t-butyl-5-methoxymethyl-6-phenyl-9-methoxy-2H-naphtho[1,2-b]pyran; and   (j) 2-(4-methoxyphenyl)-2-(2,3-dihydrobenzofuran-5-yl)-5-chloromethyl-6-methyl-9-methoxy-2H-naphtho[1,2-b]pyran.   
     
     
       6. A photochromic article comprising a polymeric organic host material and a photochromic amount of a naphthopyran compound of claim 1. 
     
     
       7. The photochromic article of claim 6 wherein the polymeric organic host material is selected from the group consisting of polyacrylates, polymethacrylates, poly( C 1  -C 12  alkyl methacrylates), polyoxy(alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. 
     
     
       8. A photochromic article comprising a polymeric organic host material and a photochromic amount of a naphthopyran compound of claim 2. 
     
     
       9. The photochromic article of claim 8 wherein the polymeric organic host material is selected from the group consisting of polyacrylates, polymethacrylates, poly( C 1  -C 12  alkyl methacrylates), polyoxy(alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. 
     
     
       10. The photochromic article of claim 9 wherein the polymeric organic host material is a solid transparent homopolymer or copolymer selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis methacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers. 
     
     
       11. The photochromic article of claim 10 wherein the photochromic compound is present in an amount of from about 0.05 to 1.0 milligram per square centimeter of organic host material surface to which the photochromic substance(s) is incorporated or applied. 
     
     
       12. The photochromic article of claim 11 wherein the article is a lens. 
     
     
       13. A photochromic article comprising a photochromic amount of the naphthopyran compound of claim 3 and a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis methacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers. 
     
     
       14. A photochromic article comprising a photochromic amount of the naphthopyran compound of claim 4 and a polymeric organic host material selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis methacrylate), poly(ethoxylated hisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers. 
     
     
       15. A photochromic article comprising, in combination, a solid transparent polymeric organic host material, and a photochromic amount of each of (a) at least one naphthopyran compound of claim 1, and (b) at least one other organic photochromic compound having at least one activated absorption maxima within the range of between about 400 and 700 nanometers. 
     
     
       16. The photochromic article of claim 15 wherein the polymeric organic host material is selected from the group consisting of polyacrylates, polymethacrylates, poly( C 1  -C 12  alkyl methacrylates), polyoxy(alkylene methacrylates), poly (alkoxylated phenol methacrylates), cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinylidene chloride), thermoplastic polycarbonates, polyesters, polyurethanes, poly(ethylene terephthalate), polystyrene, poly(alpha methylstyrene), copoly(styrene-methylmethacrylate), copoly(styrene-acrylonitrile), polyvinylbutyral and polymers of members of the group consisting of polyol(allyl carbonate) monomers, polyfunctional acrylate monomers, polyfunctional methacrylate monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, alkoxylated polyhydric alcohol acrylate monomers and diallylidene pentaerythritol monomers. 
     
     
       17. The photochromic article of claim 15 wherein the organic photochromic compound (b) is selected from the group consisting of: (a) organic photochromic substances having at least one absorption maximum in the visible range of between 400 and less than 500 nanometers;   (b) organic photochromic substances having an absorption maximum within the visible range of between about 400 and 500 nanometers and an absorption maximum within the visible range of between 500 and 700 nanometers; and   (c) organic photochromic substances having an activated absorption maxima in the visible range of greater than 570 nanometers; and   (d) mixtures of said organic photochromic substances.   
     
     
       18. The photochromic article of claim 17 wherein the organic photochromic compound (b) is an organic photochromic substances having an activated absorption maxima in the visible range of greater than 570 nanometers. 
     
     
       19. The photochromic article of claim 16 wherein the polymeric organic host material is a solid transparent homopolymer or copolymer selected from the group consisting of poly(methyl methacrylate), poly(ethylene glycol bis methacrylate), poly(ethoxylated bisphenol A dimethacrylate), thermoplastic polycarbonate, poly(vinyl acetate), polyvinylbutyral, polyurethane and polymers of members of the group consisting of diethylene glycol bis(allyl carbonate) monomers, diethylene glycol dimethacrylate monomers, diisopropenyl benzene monomers, and ethoxylated trimethylol propane triacrylate monomers. 
     
     
       20. The photochromic article of claim 17 wherein the organic photochromic compound (b) is selected from the group consisting of spiro(indoline)naphthoxazines, spiro(indoline)-pyridobenzoxazines, spiro(benzindoline)pyridobenzoxazines, spiro(benzindoline)naphthoxazines, spiro(benzindoline)naphthopyrans, spiro(indoline)benzoxazines, spiro(indoline)benzopyrans, spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans, spiro(indoline)pyrans, 3H -naphtho[2,1-b]pyrans, 2H-phenanthro[4,3-b]pyrans; 3H -phenanthro[1,2-b]pyrans; benzopyran compounds and mixtures of such photochromic substances. 
     
     
       21. The naphthopyran of claim 2 wherein: (a) R 1  is the group --C(O)Y, wherein Y is the group, --OCH(R 11 )Z, wherein R 11  is hydrogen and Z is --COOR 12 , wherein R 12  is C 1  -C 4  alkyl;   (b) R 2  is hydrogen;   (c) R 3  is C 1  -C 4  alkyl, n is 1; and   (d) B and B' are each phenyl.   
     
     
       22. The naphthopyran of claim 21 wherein R 3  is C 1  -C 2  alkyl. 
     
     
       23. The naphthopyran of claim 22 wherein R 3  is methyl. 
     
     
       24. A photochromic article comprising a polymeric organic host material and a photochromic amount of a naphthopyran compound of claim 21. 
     
     
       25. A photochromic article comprising a polymeric organic host material and a photochromic amount of a naphthopyran compound of claim 22.